3-oxa-tricyclo(4.2.1.0**2,5)nonanes



United States U.S. Cl. 260-297 13 Claims ABSTRACT OF THE DISCLOSURE Novel oxetanes having a norbornyl moiety in the molecule are prepared by the photocatalyzed reaction of norborene and a ketone, e.g., meta-benzoylpyridine to form the oXetane. An illustrative oxetane is 4-(meta-pyridyl)- 4-phenyl-3-oxatricyclo [4.21 .O ]nonane.

The present invention is directed to novel heterocyclic organic compounds and to a process for their preparation. In one aspect, this invention is directed to novel oxetanes. In a further aspect, this invention relates to certain novel oxetanes which are useful in fungicidal applications, particularly, as mildewcides.

This application is a continuation-in-part of U.S. patent application Ser. No. 324,183, now abandoned entitled Novel Oxetanes and Use Thereof filed Nov. 18, 1963 by D. R. Arnold and A. A. Sousa.

Heretofore, a wide variety of synthetic methods have been reported in the literature for the preparation of oxetanes. However, most of these methods are not very general and frequently require starting materials which are exceedingly difficult to prepare. Moreover, the reported synthetic methods rarely give high yields and hence are undesirable for large scale commercial production.

It has recently been discovered that a wide variety of novel oxetanes can be conveniently prepared by the photocycloaddition of carbonyl compounds to olefins. In many instances, the yields of the desired oxetanes are high, sometimes nearly quantitative. Moreover, the starting materials are readily available and hence oxetanes can readily be obtained which were difficult or impossible to prepare by classical methods.

Accordingly, one or more of the following objects will be achieved by the practice of the instant invention. It is an object of this invention to provide a class of novel oxetanes. Another object of this invention is to provide a class of novel oxetanes which are characterized by the presence of a norbornyl moiety in the molecule. A further object is to provide novel 4-pyridyl-4-phenyl-3-oxatricyclo [4.2.1.0 ]nonanes. Another object is to provide certain novel oxetanes which are useful in agricultural and biological applications. A still further object of this invention is to provide certain novel oxetanes which are useful as mildewcides. Another object is to provide a process for the preparation of novel oxetanes. These and other objects will readily become apparent to those skilled in the art in the light of the teachings herein set forth.

The novel oxetanes of this invention can be represented 'by the structural formula:

atent wherein R is as above, and B represents a sulfonyl group, i.e.

a lower alkylene group of from 1 to 2 carbon atoms, or an alkyl-substituted lower alkylene group of from 2 to 10 carbon atoms, (2) R and R can together with the carbon atoms to which they are attached represent ANFV j 2 Q or wherein R -R, and R and R are as above, and (3) when A is methylene, R and R are not both hydrocarbylaryl.

Preferred novel oxetanes encompassed by the aforementioned formula are those wherein A is methylene, R and R individually represent alkyl, alkenyl, aryl, alkaryl, aralkyl, cycloalkyl, bicycloalkyl, haloalkyl, haloaryl, haloalkaryl, halocarbonyl, alkoxyaryl, aminoalkyl, aminoaryl, alkylaminoalkyl, dialkylaminoalkyl, dialkylaminoalkoxyalkyl, pyridyl (ortho, meta and para), alkylpyridyl, piperidyl, piperidylalkyl, alkylpiperidyl, piperidinoalkyl, pyrimidyl, alkylpyrimidyl, pyrimidinylalkyl, pyrazolyl, pyrazyl, pyrazylalkyl, N-alkoxycarbonylpiperazinylalkyl, piperizinyl, N-alkylpiperazinylalkyl, morpholinyl, alkylmorpholinyl, 1,2,5,6 tetrahydropyridyl, N-alkyl-1,2,5,6 tetrahydropyridyl, N aryl 1,2,5,6 tetrahydropyridyl, N-aralkyl-1,2,5,6-tetrahydropyridyl, carbamyl, alkylcarbamyl, cycloalkylcarbamyl, N-heterocyclocarbamyl and the like; and R R represent hydrogen, halogen, e.g., chloro, bromo, fluoro, iodo, alkyl, alkenyl, aryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, bicycloalkyl, bicycloalkenyl, haloalkyl, haloaryl, haloalkaryl, halocycloalkyl, alkoxyalkyl, alkoxyaryl, aminoalkyl, aminoaryl, alkylaminoalkyl, dialkylaminoalkyl, dialkylaminoalkoxyalkyl and the like.

Particularly preferred oxetanes are those wherein the R variable contains up to 18 carbon atoms and wherein at least one of the R and R variables is a heterocyclic group composed of carbon, hydrogen, and from 1 to 2 ring nitrogen and/ or oxygen atoms.

Illustrative novel oxetanes encompassed by the aforementioned formula include, among others, the 4,4-dihydrocarbyl 3 oxatricyclo[4.2.1.0 ]nonanes, e.g., 4,4-dipropyl-3-oxatricyclo[4.2.1.0 ]nonane, and the like; the halogenated 4,4 dihydrocarbyl-3-oXatricyclo[4.2.1.0 nonanes, e.g., 4-chloromethyl 4 phenyl-3-oxatricyclo [4.2.1 .0 ]nonane, 4,4-di (para-chlorophenyl -3-oxatricyclo[4.2.1.0 ]nonane, and the like; the 4-hydrocarbyl-4- heterocyclyl-3-oxatricyclo[4.2.l.0 ]nonanes, e.g. 4-(ortho-pyridyl)-4-phenyl-3-oxatricyclo[4.2.1.0 ]nonane, 4- (meta-pyridyl)-4-phenyl-3-oxatricyclo[4.2.1.0 nonane, 4-(para-pyridyl)-4-phenyl 3 oxatricyclo[4.2.1.0 ]nonane, 4-methyl-4-(para-pyridyl)-3-oxatricyclo[4.2.1.0 nonane, 4-(meta-pyridyl)-4-biphenylyl 3 oxatricyclo [4.2.1.0 ]nonane, and the like; the 4,4-diheterocyclyl-3- oxatricyclo[4.2.l.0 ]nonanes, e.g., 4,4-di(rneta-pyridyl)- 3-oxatricyclo[4.2.1.0 ]nonane, and the like; the halogenated 4-hydrocarbyl 4 heterocyclyl 3 oxatricyclo [4.2.1.0 ]nonanes, e.g., 4-(para-chlorophenyl)-4-(parapyridyl)-3-oxatricyclo[4.2.l.0 ]nonane, and the like; the 4 hydrocarbyl-4-pyridyl-3-oxatricyclo[4.2.1.0 ]nonanes having substituents on one or more of the carbon atoms of the norbornane moiety, e.g., 7(8)carboxy-4- phenyl-4-(para-pyridyl)-3-oxatricyclo [4.2.1.0 nonane, and the like.

It will be readily appreciated that a wide variety of isomeric oxetanes are encompassed by the instant invention. For example, when R and R are different, two geometric isomers can be obtained for the same product:

This is, of course, in addition to the usual isomeric forms possible when the R and/or R groups are themselves heterocyclic and can be attached to the oxetane ring in more than one position. Similarly, when the R and R of the general formula are other than hydrogen, isomeric products will also be obtained.

The novel oxetanes of this invention can be produced by the photocatalyzed reaction of a ketone with an olefinic compound, e.g., bicyclo-2,2,l-heptene-2, hereinafter referred to as norbornene, or various substituted norbornene.

The reaction producing the novel oxetanes of this invention is carried out by bringing the ketone and the olefinic compound into admixture in a suitable reactor and irradiating the mixture with light energy of catalytic wavelength, typically in the range of from about 2,000 to about 4,000 Angstroms. The use of light energy of shorter wavelengths substantially below 2,000 Angstroms may engender the photolytic decomposition of the reactants and/or the oxetane product and is therefore to be avoided, while little if any of the desired reaction occurs using light energy of longer wavelengths substantially above 4,000 Angstroms. Thus, the term light energy, as employed herein, contemplates wavelengths predominantly in the ultraviolet spectrum. Convenient sources of such light energy include, for instance, tungsten bulbs, daylight, mercury vapor and xenon arc lamps, etc.

The reaction of the ketone with the olefinic compound can be carried out in solution using an inert, normally liquid solvent such as a saturated aliphatic or aromatic hydrocarbon or halogen derivative thereof, as for instance, heptane, hexane, pentane, benzene, acetic acid, acetonitrile, carbon tetrachloride, and the like, especially those having a boiling point below about 100 C. The use of such a solvent is preferred. The reaction can, however, also be carried out neat, i.e., in the absence of external solvent.

The proportion in which the reactants are utilized can vary broadly, and does not limit the invention. Typically, the reactants are employed in a proportion of from about 0.1 mole to about 10 moles of the ketone per mole of the olefinic compound. Higher or lower proportions of reactants can also be employed satisfactorily. However, the e'fiicient utilization of the reactants will generally decrease when greater than stoichiometric, i.e., equimolar, proportions are employed.

The reaction temperature can also vary broadly, typically in the range of from about 0 C. to about C., and preferably in the range of from about 10 C. to about 30 C. Here again, higher or lower reaction temperatures may also be employed satisfactorily. In any given instance, however, the temperature should not be so high as to engender the decomposition of the relatively heatsensitive oxetane product, and is dependent to a large extent upon the identity of any external solvent employed. Thus, the temperature should not be so high as to volatilize the solvent, nor so low as to preclude its normally liquid form. Preferably, the temperature should also be consistent with the dissolution of any gaseous reactant in the solvent, i.e., should not volatilize the reactant from the solvent.

When within the above temperature range, the reaction is generally carried out, i.e., irradiation continued, for a period of from several hours to several days depending upon the concentration of reactants present, the wavelength and intensity of the light energy employed, etc. Longer or shorter reaction periods sufficient to produce the desired oxetane can also be utilized. Preferably, a stoichiometric amount or excess of the olefinic compound is admixed with the ketone and the reaction is carried out to completion as determined by periodically removing aliquots from the reaction mixture and subjecting the aliquots to infra-red analysis. Under such circumstances the completion of the reaction is indicated by the disappearance of the carbonyl peak in the infra-red spectrum, carbonyl absorption occurring at a wavelength of approximately 6 microns.

Any suitable vessel which will permit the transmission of light energy of the desired wavelength, as described above, can be employed as a reactor. Typically, Pyrex or quartz vessels are employed in this regard, Pyrex being preferred interposed between the reaction mixture and the source of light energy.

Upon completion of the reaction, the oxetane product, which is believed to have an exo configuration, and is ordinarily a colorless solid and crystalline in form, can be recovered in any convenient manner. For instance, the product can be recovered as the residue obtained upon the evaporation or distillation of any unreacted material and/or solvent present. The product can thereafter be purified, if desired, by extraction or recrystallization, etc.

The apparatus employed in the preparation of the oxetanes consisted of a quartz well (Hanovia No. 19434) with a Pyrex filter immersed in a Pyrex reaction vessel having a capacity of 200 milliliters. The reaction vessel was equipped at the bottom with a glass fitted gas inlet for the introduction of purge gas and gaseous reaction, and the top with two outlets, one protected by a mercury bubbler and the other covered by a rubber septum through which periodic withdrawal of aliquots of the reaction mixture could be made. The light source was a 450 watt (Hanovia No. 679A 36) mercury arc lamp. The apparatus was maintained at a temperature in the range of 5l0 C. by immersing it in a refrigerated bath and circulating cooling water through the well.

Unless otherwise indicated, all of the oxetane products described herein were prepared by essentially the same procedure using the appropriate ketone and olefinic compound as reactants, as indicated in Table A below. In each instance, the oxetane structure of the product was confirmed by infra-red analysis, oxetane absorption occurring at a wavelength of 10: 0.3 microns, and nuclear magnetic resonance.

EXPERIMENTAL PROCEDURE A solution of 9.16 grams (0.05 mole) of meta-benzoylpyridine and 4.76 grams (0.05 mole) of norbornene in 200 milliliters of benzene was introduced into the reaction vessel and the vessel was purged with nitrogen. The

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It has also been found that the novel oxetanes of this invention are especially effective against Erysiphe polygoni, the casual organism of powdery mildew of bean and Podosphaera leucotricha, the causal organism of powdery mildew of apples. Significantly, when applied to a mildew susceptible host in a suitable inert carrier, the oxetanes, and particularly the metapyridyl substituted oxetanes, demonstrate mildewcidal activity at concentrations as low as 0.1 part per million parts of carrier, or even at somewhat lower concentrations. Moreover, the oxetanes demonstrate good retention of mildewcidal activity for appreciable periods of time following their formation.

Typically, the oxetanes are employed as mildewcides in a concentration in the range of from about 4 to about 500 parts per million parts of carrier, although higher or lower mildewcidally effective amounts can also be employed. A preferred range is from about 20 to about 100 parts per million parts of carrier. Any suitable inert liquid or solid carrier such as Water, talc, or the like, can be employed in this regard, as can readily be determined by one skilled in the art in the light of this disclosure.

The procedure employed in evaluating the novel oxetanes of this invention is as follows:

BIOLOGICAL TEST PROCEDURES A stock suspension of the oxetane was prepared by dissolving one gram in 50 milliliters of acetone in which had been dissolved 0.1 gram of octylphenoxy polyethoxyethanol as an emulsifying agent. The resulting solution the stock suspension above was also sprayed on other infected plants.

After the spray had dried, the plants were held in a greenhouse for a period of 7-70 days. At the end of this period, visual observations of mildew control were made according to the following designations:

5=100% control, no spots per leaf 4: 1-3 spots per leaf 3:4-10 spots per leaf 2=Many but distinctly different spots 1=Leaf overrun with mildew; equal to check plants.

In a similar procedure, MacIntosh apple seedlings were used as the host plant for the apple mildew, Podosphaera leucotricha. The seedlings were inoculated twenty-four hours prior to initial spraying with a stock solution prepared a described above. Spraying was carried out as described above at weekly intervals for a period of three weeks. Visual observations of mildew control were made one week following each application in accordance with the designations set forth above. The treated plants were placed among untreated, heavily mildewed apple seedings during the entire test period except for the time required for spraying.

The results obtaind using the oxetane product of Example 8, viz 4 (meta pyridyl) 4 phenyl-3-oxatricyclo- [4.2.1.0 ]nonane, as the mildewcide are tabulated below in Tables B and C. Table B is concerned with the use of the oxetane as a bean mildew eradicant while Table C is concerned with the use of the oxetane as an apple mildew eradicant. The effectiveness rating is that made in accordance with the visual observations described above. The concentrations are in parts of mildewcide per million parts of carrier.

TABLE B was m1xed into 150 m1ll1l1ters of water to give 200 m1l- 001mm Efiectiveness Rating 11l1ters of a suspenslon containing the oxetane 1n finely tratlon, divided form. The various test concentrations described Testl in parts per million were prepared by dilution of this stock Mildewcide: solution Oxetane of Example 8 22 g g 2 Tender green beans were used as the host plant for the 3.2 i 4 4 bean mildew, llrysiphe polygom. A culture of this or- Karathane 5 "5 "5 ganisrn was maintained on bean plants in a greenhouse. 4 2 2 2 Twenty-four hours prior to testing, unifected plants with 8:2 1 primary leaves fully expanded were inoculated by brush- TABLE 0 Effectiveness Rating C0ncen First Week Second Week Third Week tration, jp.p.m. Test 1 Test 2 Test 1 Test 2 Test 1 Test, 2

Mlldewcide:

Oxetaue of Ex. 8 500 5 5 5 5 5 5 100 5 5 5 5 5 5 20 5 5 4 4 4 4 4 3 5 2 3 2 3 Karathane 500 5 5 5 5 5 5 100 5 5 4 5 4 3 20 3 5 3 3 a 2 4 2 4 2 2 1 5 ing their leaves lightly with plants taken from the stock culture.

The bean plants infected with mildew were sprayed on a revolving turntable for 30 seconds at a pressure of 40 p.s.i.g. Approximately 100 milliliters of spray were delivered. For control purpose, an equal volume of a water solution containing acetone emulsifier, and a conventional mildewcide, Karathane in the same concentrations as 2,4-dinitro 6 (2-octyl) phenyl crotonnte.

'17 control of mildew. Thus derived, the ED values were found to be as follows:

Mildewcide: ED Oxetane of EX. 8 0.8 Oxetane of Ex. 7 100 Oxetane of Ex. 9 40 Oxetane of Ex. 10 100 In addition to contacting the causative organism, mildew control is also realized by the application of the oxetanes of this invention in similar manner to an uninfected mildew susceptible host. Protection against the onset of mildew is thereby realized for appreciable periods of time during which the oxetanes are active as mildewcides.

Moreover, it has been found from screening tests that the oxetanes of this invention, particularly the metapyridyl substituted oxetanes, are effective in other fungicidal applications. By way of illustration, the oxetane of Example 8 has also demonstrated activity as a soil fungicide, Pythium sp. being the causative organism in this instance.

It has also been observed that the oxetane of this invention are useful in the control of two foliar diseases, tomato early blight (Alternaria solani) and cucumber andthracnose (Colletotorichum lagenarium). The composition of Example 8 was tested for these diseases in the following manner.

The casual organism of tomato early blight is cultured on potato dextrose agar at a temperature of 20 C. Transfers are made to Petri dishes 8 days prior to testing and scraped and irradiated with ultraviolet for one minute one day prior to testing.

One tomato plant variety Bonny Best of a standard age and height is sprayed on a revolving turntable. A 100-110 ml. volume of the formulated water mixture of chemical (I) is applied to each plant with a DeVilbiss spray gun, air pressure set at 40 pounds Application of this volume of spray takes 25 seconds. The potted plants are then placed in an 8 ounce waxed cup. An additional 40 ml. volume of test formulation (II) is watered into the soil for determination of systemic activity. Similar applications to other plants are made with a water solution containing acetone and emulsifier in the same concentration as the test mixture but without the candidate pesticide. These plants are untreated checks or controls for the experiment. As soon as the spray has dried, the plants are inoculated by again placing them on the turntable and spraying with a spore suspension of early blight (containing 12,000- 15,000 spores per ml. of water) for 30 seconds at 20 pounds pressure.

The test compound was formulated by a standard procedure of solution in acetone, addition of an emulsifier, and dilution with water. Primary topical applications are conducted at 10 p.p.m. (I) and systemic tests at 250 p.p.m.

Following inoculation the plants are incubated for 24 hours at 70 F. and 100 percent relative humidity. The plants are then removed from the incubation chamber and held for an additional 24 hours at room temperature.

The degree of infection is visually rated according to the following designations:

=no lesions (perfect control) 4=very few lesions 3=moderately infected 1=rnany lesions, equal to untreated control plants The results obtained using the oxetane product of Example 8 and a known fungicide are tabulated in Table D below:

TAB LE D Efiectiveness Rating Concentration, p.p.m.

Zinc ethylene bisdithiocarbamate The causal organism of cucumber anthracnose is cultured on freshly prepared lima bean agar. One' week following inoculation pink spore masses are formed. An aqueous suspension containing 200,000-500,000 spores per ml. is prepared as inoculum.

Cucumber plants 24 weeks of age are the host plants. The plants are grown in 3 inch pots. Two plants per pot are sprayed on a revolving turntable. A 100-110 ml. volume of the formulated water mixture of the chemical is applied to the plants with a DeVilbiss spray 'gun with air pressure set at 40 pounds p.s.i. Application of this volume of spray takes 25 seconds. An equal volume of a water solution containing acetone and emulsifier in the same concentrations as the fungicidal mixture but without the candidate fungicide is also sprayed on 4 cucumber plants which are held as untreated checks or controls. As soon as the spray has dried, the plants are inoculated by again placing them on the turntable and spraying with the spore suspension of anthracnose for 30 seconds at 20 pounds p.s.i.

The test compounds are formulated by a standard procedure of solution in acetone, addition of an emulsifier, and dilution with water. Initial tests are conducted at 100 p.p.m.

Following inoculation the plants are incubated for 24 hours at 70 F. and 100 percent relative humidity. The plants are then removed from the incubation chamber and held at F. and 50 percent relative humidity until symptoms of disease develop.

One week after inoculation counts are made of the total number of lesions found on the primary leaves of each plant, treated and untreated. The percent control is calculated, and results arereported according to the following designations:

5=90l00% control 4=70-89% control 3=50'6 9% control 2=2549% control 1=0-24% control The results obtained using the oxetane product of Example 8 and a known fungicide are tabulated in Table E below:

TAB LE E Concen- Effectivetration, ness p.p.m. Rating Compound:

Oxetane of Example 8 500 4 1 20 1 4 1 Manganese bisdithiocarbamate 500 100 5 20 3 4 2 with other reactive cyclic monomers to provide a useful class of polymeric compounds. These polymers can range from various liquids to tough solids. The viscous liquids of relatively low molecular weight, are useful in the preparation of polishes and waxes and as thickening agents for various lubricants. The polymers can also be employed as protective coatings and are useful for the production of various shaped articles such as brush handles, buttons, and the like. Moreover, since many of the compositions of this invention contain desirable functional groups, they are particularly useful in those areas where it is desirable to build such groups into the polymeric network.

Illustrative cyclic monomers which can polymerize with the oxetanes of this invention include, among others, the epoxides, such as 4-vinylcyclohexene dioxide, 3,4 epoxycyclohexyl, 3,4 epoxycyclohexylcarboxylate, bis(2,3-epoxycyclopentyl)ether, and the like. Polymerization can be effected in the presence of known epoxide polymerization catalysts according to accepted techniques.

What is claimed is:

1. The oxetane of the formula:

wherein A is methylene, R R are hydrogen and R and R are propyl.

3. The oxetane of the formula:

wherein A is methylene, R -R are hydrogen, R is phenyl and R is pyridyl.

4. The oxetane of the formula:

wherein A is methylene, R R are hydrogen, R is phenyl and R is ortho-pyridyl.

5. The oxetane of the formula:

wherein A is methylene, R R are hydrogen, R is phenyl and R is meta-pyridyl.

6. The oxetane of the formula:

wherein R R are hydrogen, R is phenyl and R is parapyridyl.

7. The oxetane of the formula:

wherein R 'R are hydrogen, R is methyl and R is metapyridyl.

8. The oxetane of the formula:

wherein R is methyl and R is para-pyridyl and R -R are hydrogen.

9. The oxetane of the formula:

wherein A is methylene, R R are hydrogen, R is phenyl and R is N-loweralkyl-1,2,5,6-tetrahydropyridyl.

10. The oxetane of the formula:

21 22 wherein A is methylene, R R are hydrogen, R is phenyl References Cited and R is n-methyl-1,2,5,6-tetrahydropyridy1. Scharf et a1., Tetrahedron Letters, June 1963, pp.

11. 4 phenyl 4 haloloweralkyl 3 oxatricyclo 821-3 [4.2.1.0 ]nonane. 5 HENRY R. JILES, Primary Examiner.

12. 4 phenyl 4 chlorornethyl 3 oxatricyclo ALAN L. ROTMAN, Assistant Examiner [4.2.1.0 ]n0nane. CL

4 Phenyi 4 (N methyl 135,6 tetrahydro' 204-162; 260247.2, 247.7, 251, 268, 294.5, 295, 310, pyr1dy1)-3-0Xatr1cyc10[4.2.1.0 ]n0nane- 10 328, 515; 424- 24s, 251, 256, 263, 266, 267, 27s 

